CN104250820A - Method and apparatus for regenerating all acid of stainless steel pickling waste liquid - Google Patents
Method and apparatus for regenerating all acid of stainless steel pickling waste liquid Download PDFInfo
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Abstract
The invention relates to a method and an apparatus (BSTAR for short) for regenerating all acid of stainless steel pickling waste liquid, the method comprises the following steps: 1)storing and depositing waste acid, 2) aerating, cooling and crystallizing the waste acid; 3)nanofiltrating and processing free waste acid, 4)spraying and roasting a crystal substance, 5)recovering by an absorbing tower, 6)absorbing acid for backflow and adjusting, 7)storing recovered acid, and 8)processing iron oxide powder and processing tail gas. The method employs a separation treatment technology of crystal substance fluoride and free waste acid, and has the characteristics of less nitric acid amount which participates in roasting, NOX generation amount is less, nitric acid recovery rate is high, operation cost of a nitrogen removal apparatus is low; a selectivity backflow adjusting technology of recovered acid can change the composition content in waste acid, and has wide adaptability for processing various series of stainless steel waste acid solutions; the method has high recovery rate of all acid, reutilization rate of the recovered acid is high, waste acid solution discharge is less, technology equipment is simple and reliable, the system operation and maintenance cost are low, and the method and apparatus have wide popularization and application prospect.
Description
[technical field]
The present invention relates to a kind of acid regeneration environmental protection and energy saving technology removing metal ion in complete series waste acid from stainless steel acid washing, the Environmental-protection energy-saving method that the acid-washing waste acid that particularly a kind of complete series stainless steel adopts nitric acid and hydrofluoric acid pickling to produce utilizes after carrying out regenerating recovery.
[background technology]
Prior art one: spray roasting technology (see " bao steel technology " supplementary issue-cold-rolling stainless steel acid-washing waste acid roasting method recovery technology commentary, " bao steel technology " 6th phase in 2005-waste acid from stainless steel acid washing roasting regeneration system trouble analysis and countermeasure in 2003) and Fig. 1.In order to regenerate nitric acid in waste acid from stainless steel acid washing and hydrofluoric acid, spray roasting technology by all spent acid solutions first through initial concentration and dehydration, then all spent acid are all injected in calcination stove and carry out roasting, calcination stove mixed gas out enters in washing tower and absorption tower, is undertaken absorbing finally forming regenerating acid by atomized water spray; Brown iron oxide bottom stoving oven packs through pelletizer, and tail gas enters nitrogen rejection facility and carries out discharge pre-treatment.The advantage of this technology is that Equipments Setting is succinct, easy to maintenance, and system cloud gray model is reliable, the strong adaptability of the stainless steel grade of complete series.Shortcoming carries out concentrated and roasting to all spent acid on the one hand, consumes a large amount of combustion gas equal energy sources; On the other hand as the NO that a large amount of nitric acid is formed after roasting
xbe difficult to be absorbed by absorption tower, the therefore rate of recovery of nitric acid extremely low (less than 50%).And a large amount of NO in tail gas
xneed to consume a large amount of catalytic reducer (ammonia) process up to standard after could discharge.Therefore, it is high that this spray roasting technology has running cost, the defect that the nitric acid rate of recovery is low.
Prior art two: STAR technology is (see " application of the 7th (2009) China Steel nd Annual Meeting collection-nanofiltration in nitration mixture regeneration system rapidly " and Fig. 2.First this technology adopts carries out micro-filtration and nanofiltration process to acid-washing waste acid, is separated wherein free nitric acid and hydrofluoric acid, carries out metal ion interception simultaneously; The concentrated solution of nanofiltration carries out Freeze crystallization, crystallisate is entered calcination stove and carries out roasting after being dewatered by belt filter, enter sack cleaner after the gas of roasting is regulated by temperature, then enter absorption tower, by spraying penetrating fluid that nanofiltration generates or water generates regenerating acid.Go out brown iron oxide bottom sack cleaner, the tail gas that absorption tower cannot absorb enters air after entering denitrogenation and defluorinate treatment unit.The design philosophy of this technology is by a large amount of free acid of nanofiltration separation, and then crystallization roasting, greatly can reduce the energy consumption of combustion gas during operation, improve the rate of recovery of nitric acid simultaneously.This technology, due to the demand of crystallization, has high requirements for the content of fluoride ion in spent acid solution, but when actual motion owing to producing the diversity of steel grade, cause the complicated of spent acid solution changeable, content of fluoride ion is lower and unstable.Facts have proved of domestic unique employing STAR technical finesse waste mixed acid, due to the feature that continuous change and the stainless steel enterprises tissue in market are produced, the stainless steel kind of producing is tied to 400 from BN system, 300 and is, and switch frequent, point kind cannot be adopted to carry out classifying the mode of recycling, and the complicated that therefore result in waste mixed acid is changeable, and requirement when definitely cannot reach design at all, in a large amount of waste mixed acid free hydrofluoric acid and total fluorion very low, even do not have.Therefore, when producing AISI200 system and AISI400 series stainless steel, because during pickling, the concentration of hydrofluoric acid is lower, Fe (NO in metal-salt in spent acid
3)
3and FeF
3ratio between molar weight becomes 60%: 40% from 20%: 80%, that is FeF in spent acid
3ratio be produce AISI300 series 50%, cause in waste mixed acid containing Fe (NO
3)
3concentration is higher, and only has metal fluoride can crystalline deposit in evaporative crystallization, and nitrate substantially can not crystallization in evaporation and crystal process, cannot the nitrate of crystallization cause spray roasting amount to add about 3 times; Meanwhile, because the interception rate of nanofiltration membrane to metal ion only has 20 ~ 30%, the concentration of metal ions in regenerating acid is finally caused to be difficult to up to more than 23% (even reaching 38.5g/l) recycle.The distinct disadvantage of this technology is not strong for the spent acid solution process practicality of complete series steel grade.
On the one hand the usefulness of spent acid solution composition on nanofiltration, freezing and crystallizing and spray roasting creates direct impact, when being stainless steel production for 300, effect is better, but for other be and to mix steel grade production effect very poor, result is concentration of metal ions severe overweight in recovered acid, recovered acid is difficult to the requirement reaching recycling, or because of the recycling timed interval too short frequent complex acid, causes the serious imbalance of acid and arrange outward, sludge disposal expense is finally made sharply to increase, running cost superelevation.On the other hand because the configuration of STAR technical equipment is complicated, particularly in order to improve system heat exchange or withstand voltage effect and the equipment of the alloy material adopted, not only easy corrosion damage but also expensive, finally cause system maintenance difficulty and run being difficult to stable, cost of equipment maintenance is very high.Therefore this technology is difficult to the advantage embodying its comprehensive cost.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, a kind of full acid regeneration method and device of stainless steel acid-washing waste liquid is provided.
The object of the invention is to be achieved through the following technical solutions:
A kind of full acid regeneration method (being called for short BSTAR) of stainless steel acid-washing waste liquid, it is characterized in that, concrete technology flow process mainly comprises: (1) spent acid stores and precipitation, (2) spent acid aeration freezing and crystallizing, (3) free spent acid nanofiltration process, (4) crystallisate spray roasting, (5) absorption tower is reclaimed, (6) absorb acid backflow to regulate, (7) regenerating acid stores, the process of (8) brown iron oxide and vent gas treatment; Wherein, after waste mixed acid is entered in spent acid storage tank carried out storing and precipitate by valve, then freezing and crystallizing tank and temperature control surge tank is entered into; Throw out on the one hand in spent acid storage tank, the throw out of the fluorochemical in freezing and crystallizing tank and temperature control surge tank all enters into setting tank, then sends into stoving oven; On the other hand the spent acid of temperature control surge tank enters nitric acid that nano-filtration unit carries out dissociating and is separated and obtains concentrated solution and penetrating fluid, concentrated solution enters spent acid storage tank and freezing and crystallizing tank processes repeatedly, and penetrating fluid is used for the recovery of hydrofluoric acid gas in absorption tower or directly sends into recovered acid tank; Throw out obtains hydrogen fluoride gas at roasting kiln roasting, again the hydrogen fluoride gas of generation is entered into different absorption towers, generate the very high recovered acid of hydrofluoric acid concentration at top, absorption tower spray pure water or carry out absorbing the high regenerating acid of generation concentration of nitric acid at top, absorption tower spray nanofiltration penetrating fluid; The regenerating acid that hydrofluoric acid containing concentration is high is back to spent acid storage tank and freezing and crystallizing tank also or directly enters regenerating acid tank for concentration adjustment; The recovered acid of different components concentration is obtained by configuring multiple recovered acid tank; Spent acid storage tank and freezing and crystallizing tank can be back to the recovered acid that the absorption tower that hydrofluoric acid gas reclaims generates with pure water; The burning iron powder generated bottom stoving oven carries out pack process by pelletizer, and the tail gas that absorption tower cannot absorb carries out discharge pre-treatment by denitrogenation defluorinate treatment unit.
(1) spent acid stores and precipitation
Spent acid tanks portion adopts little volume, and multiple tank gradient is arranged, flow regime step by step; Top adopts negative pressure-pumping, send absorption tower by acid mist; Acid solution tank bottom band abrupt slope, arranges multilayer aerating apparatus apart from bottom certain altitude in each storage tank and is beneficial to the grid blocking apparatus of deposition, realizes the progressively precipitate and separate of useless mixed liquid Middle molecule and higher level particulate matter.
(2) spent acid aeration freezing and crystallizing
By the temperature difference and low temperature aeration system in spent acid storage tank, improved the oxidation of metal ion in spent acid solution on the one hand by aeration agitation, increase the nuclei of crystallization in waste liquid; Aeration agitation can realize the abundant combination of fluorion and metal ion on the other hand, under control freezing temp, fluorion and metal ion crystallization are generated fluorochemical, under the condition with abundant fluorion, more than 90% metal object can be realized and metal ion realizes flash liberation from spent acid.Therefore, the conservative control of fluorion amount and temperature is the key point of this operation.Crystallization reaction is schematically as follows:
4Fe
3++3O
2→2Fe
2O
3
2Fe
3++6F
-+3H
2O→2FeF
3x3H
2O
Cr
3++3F
-+3H
2O→CrF
3x3H
2O
Ni
2++2F
-+3H
2O→NiF
2x3H
2O
Mn
2++2F
-+4H
2O→MnF
2x4H
2O
Mo
6++6F
-+3H
2O→MoF
6x3H
2O
Adopt freezing and crystallizing method, by changing original high temperature evaporation crystallization processes and changing Crystallization Procedure configuration, make in spent acid solution, to have sufficient crystallising core.Because high temperature evaporation crystallization cannot form precipitation for nitrate, the technology in past adopts all spent acid solution evaporative crystallizations, not only causes crystalline rate not high because component ratio each in spent acid solution fails optimization, and needs the energy of at substantial.
Adopt the technology that refrigerator and blower fan combine, generate the cooling gas being used for system and needing, the flow of cooling gas and temperature can be optimized according to the demand of system.This technology, owing to eliminating the interchanger type of cooling contacted with nitration mixture, not only reduces system configuration and maintenance cost, and improves the accessibility of maintenance, greatly improves cooling system reliability of operation and stability.
This Technology adopts the synchronous treatment process in parallel of free waste nitric acid and hydrofluoric acid.Enter the material of setting tank mainly based on fluorochemical and impurity after freezing and crystallizing and precipitation, lower operation enters stoving oven and carries out roasting.A large amount of spent acid based on nitric acid on freezing and crystallizing top contain a small amount of free metal ion, enter and include the secondary separation that operation carries out metal ion in.
(3) free spent acid nanofiltration process
Adopt nanofiltration to the free secondary separation taking nitric acid as the spent acid of main component and carry out ion, nanofiltration penetrating fluid generates the high regenerating acid of concentration of nitric acid.Nanofiltration membrane for free nitric acid rate of permeation between 80 ~ 95%, for metal ion interception rate optimal zone between 20% ~ 30%.Nanofiltration membrane to the law of segregation of ion is: for negatively charged ion, and rate of permeation is successively decreased NO in the following order
3-, Cl
-, OH
-, SO
2-, CO
3-; For positively charged ion, the order that rejection increases progressively is K
+, Ca
2+, Mn
2+, Cu
2+, Ni
2+, Cr
3+, Fe
3+, Mo
6+; Monovalent ion permeates, and polyvalent ion has delay.By controlling cycling rate, the pressure and temperature of nanofiltration, the clearance of metal ion can be controlled about 30%.
The pressure-controlling of nanofiltration system is at 4MPa, and high pressure fluid infusion pump can adopt the boost version of two-step supercharging, and recycle pump adopts in-line pump form, and this technology can reduce difficulty and the maintenance cost of nano-filtration unit manufacture further.High pressure fluid infusion pump and recycle pump adopt the metallic substance manufacture of resistance to nitration mixture.
(4) crystallisate spray roasting
Enter stoving oven and carry out the throw out of calcination process based on fluorochemical, after roasting, mainly generate hydrogen fluoride gas.Due to main roasting throw out, therefore roasting amount greatly reduces, and effectively reduces the energy consumption of system.Calcination is schematically as follows:
H
2O
(L)→H
2O
(G)
HF
(L)→HF
(G)
HNO
3(L)→HNO
3(G)
2FeF
3x3H
2O
(S)→Fe
2O
3(S)+6HF
(G)+3H
2O
(G)
2CrF
3x3H
2O
(S)→Cr
2O
3(S)+6HF
(G)+3H
2O
(G)
NiF
2x3H
2O
(S)→NiO
(S)+2HF
(G)+2H
2O
(G)
4MnF
2x4H
2O
(S)+O
2→Mn
2O
3+8HF
(G)+4H
2O
(G)
MoF
6x3H
2O
(S)→MoO
3+6HF
(G)+3H
2O
(G)
Wherein subscript: L=liquid, G=gas, S=solid
(5) absorption tower is reclaimed
In the recycling step of absorption tower, the hydrogen fluoride gas that roasting generates enters absorption tower and absorbs, and generates recovered acid; When adopting de-salted water to carry out spray absorber, the regenerating acid of generation is based on hydrofluoric acid; When adopting the penetrating fluid of nanofiltration to carry out spraying recovery, the nitration mixture of nitric acid and hydrofluoric acid will be generated.
The hydrogen fluoride gas that roasting generates enters absorption tower and absorbs, and generates hydrofluoric acid.When adopting de-salted water to carry out spray absorber, the regenerating acid of generation, based on hydrofluoric acid, can be used for backflow and regulates; When adopting the penetrating fluid of nanofiltration to carry out spraying recovery, the nitration mixture of nitric acid and hydrofluoric acid will be generated.Arrange two absorption towers during preferred plan, utilize de-salted water and nitric acid to carry out spray absorber respectively, recovered acid can be configured utilization as required.
(6) absorb acid backflow to regulate
In absorption acid backflow regulating step, the gas that roasting generates generates the high regenerating acid of hydrofluoric acid concentration after Selective absorber tower absorbs, be back to spent acid storage tank and freezing and crystallizing tank, by regulating the fluorinion concentration in spent acid storage tank and freezing and crystallizing tank after the regenerating acid backflow that hydrofluoric acid containing concentration is high.
The gas that roasting generates generates the high regenerating acid of hydrofluoric acid concentration after Selective absorber tower absorbs, be back to spent acid storage tank and freezing and crystallizing tank, by the regenerating acid backflow that hydrofluoric acid containing concentration is high, the concentration of fluorion in regulating and controlling spent acid, to realize the demand of metal ion crystallization, thus waste acid regenerating system is made to produce benign cycle.
(7) regenerating acid stores
The storage tank of regenerating acid can adopt three tank forms, deposits high concentration of hydrofluoric acid recovered acid for one, deposits the high recovered acid of concentration of nitric acid for one, deposits nitric acid and the acid of hydrofluoric acid mixed regeneration for one.This Technology has the regenerating acid of three kinds of concentration compositions, has adaptability widely for concentration configurations different during recycling.
(8) process of brown iron oxide and vent gas treatment
The burning iron powder that calcination furnace bottom generates is packed by pelletizer.The tail gas that absorption tower cannot absorb enters denitrification processing device, after environment protection standard, discharge air
HF
(G)→HF
(L)
Ca(OH)
2+2HF→CaF
2+2H
2O
2NO+1/2O
2+2NH
3→2N
2+2H
2O
All breakout tanks that whole system exists the temperature difference all must carry out isothermal holding, arrange backwashing device simultaneously, with the phenomenon that cannot clear up after crystallisate blocking pipe in preventing from carrying and precipitation.
The present invention also provides it mainly to comprise spent acid storage tank, freezing and crystallizing tank, temperature control surge tank, recovered acid tank, absorption tower and stoving oven; It is characterized in that, spent acid storage tank is connected with freezing and crystallizing tank by pipeline, freezing and crystallizing tank is connected with temperature control surge tank by pipeline, temperature control surge tank is connected with recovered acid tank respectively by high pressure fluid infusion pump and recycle pump, recovered acid tank is connected with spent acid storage tank with absorption tower by pipeline, absorption tower is connected with stoving oven by pipeline, and stoving oven is connected by the out of stock device of pipeline and desulfurization, and stoving oven is connected with brown iron oxide collection device by pipeline.
Described temperature control surge tank is connected with setting tank by pipeline.
Pass through the present invention, form that a kind of system device is stable, nitric acid and the hydrofluoric acid rate of recovery is high, the adaptable Technology of complete series waste acid from stainless steel acid washing, the technology of above-mentioned two kinds of former external imports can be substituted completely and there is more superior performance and have more extensive generalization; Its innovative point is as follows:
(1) the present invention adopts the control techniques of the backflow waste acid pot of the recovered acid based on hydrofluoric acid gas after roasting and freezing and crystallizing tank, the concentration of hydrofluoric acid ion in adjustable spent acid, creates the favourable condition of fluoride crystal in the sufficient situation of the nuclei of crystallization; Improve the adaptability of this technology for complexity composition acid washing liquid for stainless steel;
(2) the present invention adopts the method at spent acid storage tank and the cooling of freezing and crystallizing pot bottom aeration, frozen gas is supplied by blower fan, aeration tube adopts nonmetal as PVDF material, create the high temperature difference environment that fluoride crystal needs on the one hand, avoid metal material to contact with spent acid solution, reduce refrigeration system device fabrication cost and failure rate.On the other hand by aerating apparatus, by abundant stirring, improve ferrous ions oxidation to improve crystalline rate;
(3) the present invention is configured in front operation after freezing and crystallizing and precipitation technology being combined, calcination stove mainly processes crystalline deposit fluorochemical, metal ion in the main separated free acid again of nanofiltration, the treatment capacity of corresponding subsequent handling reduces greatly, reduces energy consumption cost during system cloud gray model;
(4) due to nitrate not easily crystallization, therefore adopt crystallization fluorochemical to carry out hydrofluoric acid concentration in the gas of roasting generation high, concentration of nitric acid is low.The regenerating acid that independent reclaiming process reclaims requires to have stronger adaptability for different complex acid components when utilizing;
(5) the crystallization fluorochemical of the present invention's employing and the separately treatment technology of free acid, have the advantages that the nitric acid amount of participation roasting is few, therefore NOX produces few, the advantage that the rate of recovery of nitric acid is high, nitrogen rejection facility running cost is low;
(6) to have full acid recovering rate high in the present invention, and recovered acid reuse ratio is high, and spent acid solution discharge is few, and technical equipment is succinctly reliable, and system cloud gray model and the low advantage of maintenance cost, have more wide popularizing application prospect.
(7) consider that stainless steel product price is high, consumption is less, particular requirement is many, the tissue caused produces the feature that single output is few, description is many.When the crew qiting of enterprises of producing stainless steel is less, single fighter output is large, be difficult to point specification kind tissue when producing, and be difficult to recycling because technique adjustment switches frequent, the three wastes, the imagination that the scale of resulting through reduces costs will become it on the contrary and bear.How to reduce the production cost of the large unit of design output further, improve acid-washing waste acid recovery utilization rate, thus the consumption of reduction eo-acid is also one of approach.
[accompanying drawing explanation]
Fig. 1: spray roasting technology schematic diagram;
Fig. 2: STAR technology schematic diagram;
Fig. 3: BSTAR techniqueflow chart.
[embodiment]
The full acid regeneration method of a kind of stainless steel acid-washing waste liquid of the present invention and the embodiment of device are below provided.
Embodiment 1
According to BSTAR technology of the present invention, composition graphs 3, provides a kind of implementation method of main flow below:
Spent acid tanks portion adopts large volume, multiple tank gradient layout, top tape negative pressure is inhaled mist and sent absorption tower, in bottom belt abrupt slope, each tank, aerating apparatus and grid blocking apparatus are set apart from bottom certain altitude, the bottom of storage tank adopts pyramidal fashion, aerating apparatus is arranged on the inner circular periphery of storage tank and on the top of grid device, solarization air cap direction adopts and upwarps the function that form has stirring simultaneously.In one-level storage tank, a set of aerating apparatus from calcination furnace gases is circumferentially set again at middle part.The sludge pump of cold air aerating apparatus and tank bottom adopts discontinuous mode of operation, and aerate flux can regulate.Temperature and Level Detection is all provided with in all spent acid storage tanks.
The cold air of 1-5 DEG C that is produced by compressor sends into cold air aerating apparatus by blower fan, aerating oxidation crystallization is carried out in spent acid storage tank, realize the function of the crystallisation by cooling of fluorochemical, particulate matter and crystallisate gradient aging precipitation, each spent acid tank bottom throw out sends into setting tank respectively.The chain control of temperature detected in refrigerant condenser and blower fan and storage tank.
Final stage waste mixed acid liquid is adjusted to after normal temperature (15-20 DEG C) through excess temperature and sends into nano-filtration unit process, temperature in storage tank controls to adopt steam and cold wind to regulate, nano-filtration unit adopts two sections of pressuring methods to form the high pressure of 38MPa, recycle pump adopts in-line pump form, lift is 0.2MPa, the pump case of two kinds of pumps can adopt alloy material, and the consumable accessory such as impeller and sealing adopts the process of spraying acid-resistant layer, is convenient to the replacing of consumable accessory.The designing treatment amount of nano-filtration unit is the spent acid liquid measure of 70%-80%, the flow divider valve of configuration adopts manual modulation valve to add the mode of micrometeor variable valve combination, also stopping valve can be adopted to add the combination of variable valve, two covers are set and the same one standby, to improve the work-ing life of pressure and flow divider valve.Nano-filtration unit adopts the mode of regularly mending discharge opeing to run, and the concentrated solution after nanofiltration sends back to one-level spent acid storage tank and again carries out pre-treatment, and penetrating fluid enters down operation according to demand.
The clear liquor at setting tank top adopts gravity to overflow back and flows to one-level spent acid storage tank, be delivered to the spray gun of stoving oven with sludge pump after the redeposition of bottom, processed in calcination stove (temperature 600-700 DEG C) by spray gun, the designing treatment amount of stoving oven is 50%-60% spent acid liquid measure.
Other a set of aerating apparatus of spent acid storage tank is sent in the gas part backflow at stoving oven top, a part is sent absorption tower 2 to carry out absorption and is generated regenerating acid, two portions flow can pass through governor valve control sendout, mainly fully can form crystallisate in spent acid storage tank for priority condition.The burning iron powder that calcination furnace bottom generates is packed by pelletizer.The tail gas that absorption tower cannot absorb enters denitrification processing device, after environment protection standard, discharge air.
All breakout tanks that whole system exists the temperature difference all must carry out isothermal holding, arrange backwashing device simultaneously, regularly carry out back flushing or stirring, with the phenomenon that cannot clear up after crystallisate blocking pipe in preventing from carrying and precipitation.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (10)
1. the full acid regeneration method of a stainless steel acid-washing waste liquid, concrete technology flow process mainly comprises: (1) spent acid stores and precipitation, (2) spent acid aeration freezing and crystallizing, (3) free spent acid nanofiltration process, (4) crystallisate spray roasting, (5) absorption tower is reclaimed, and (6) absorb acid backflow and regulate, (7) regenerating acid stores, the process of (8) brown iron oxide and vent gas treatment; It is characterized in that, the spent acid of temperature control surge tank enters nitric acid that nano-filtration unit carries out dissociating and is separated and obtains concentrated solution and penetrating fluid, concentrated solution enters spent acid storage tank and freezing and crystallizing tank processes repeatedly, and penetrating fluid is used for the recovery of hydrofluoric acid gas in absorption tower or directly sends into recovered acid tank; Throw out obtains hydrogen fluoride gas at roasting kiln roasting, then the hydrogen fluoride gas of generation is entered into different absorption towers, obtains the recovered acid of different components concentration by configuring multiple recovered acid tank; Spent acid storage tank and freezing and crystallizing tank can be back to the recovered acid that the absorption tower that hydrofluoric acid gas reclaims generates with pure water; The burning iron powder generated bottom stoving oven carries out pack process by pelletizer, and the tail gas that absorption tower cannot absorb carries out discharge pre-treatment by denitrogenation defluorinate treatment unit.
2. the full acid regeneration method of a kind of stainless steel acid-washing waste liquid as claimed in claim 1, is characterized in that, in spent acid stores and precipitates, spent acid tanks portion adopts multiple tank gradient to arrange, flow regime step by step; Top adopts negative pressure-pumping, send absorption tower by acid mist; Acid solution tank bottom band abrupt slope, arranges multilayer aerating apparatus and the grid blocking apparatus being beneficial to deposition in each storage tank.
3. the full acid regeneration method of a kind of stainless steel acid-washing waste liquid as claimed in claim 1, it is characterized in that, in free spent acid nanofiltration treatment step, adopt nanofiltration to the free secondary separation taking nitric acid as the spent acid of main component and carry out ion, nanofiltration penetrating fluid generates the high regenerating acid of concentration of nitric acid; Nanofiltration membrane for free nitric acid rate of permeation between 80 ~ 95%.
4. the full acid regeneration method of a kind of stainless steel acid-washing waste liquid as claimed in claim 3, it is characterized in that, the pressure-controlling of nanofiltration system is at 4MPa, high pressure fluid infusion pump adopts the boost version of two-step supercharging, recycle pump adopts in-line pump form, and high pressure fluid infusion pump and recycle pump adopt the metallic substance manufacture of resistance to nitration mixture.
5. the full acid regeneration method of a kind of stainless steel acid-washing waste liquid as claimed in claim 1, is characterized in that, in crystallisate spray roasting step, enters stoving oven and carries out the throw out of calcination process based on fluorochemical, after roasting, mainly generate hydrogen fluoride gas.
6. the full acid regeneration method of a kind of stainless steel acid-washing waste liquid as claimed in claim 1, is characterized in that, in the recycling step of absorption tower, the hydrogen fluoride gas that roasting generates enters absorption tower and absorbs, and generates recovered acid; When adopting de-salted water to carry out spray absorber, the regenerating acid of generation is based on hydrofluoric acid; When adopting the penetrating fluid of nanofiltration to carry out spraying recovery, the nitration mixture of nitric acid and hydrofluoric acid will be generated.
7. the full acid regeneration method of a kind of stainless steel acid-washing waste liquid as claimed in claim 1, it is characterized in that, in absorption acid backflow regulating step, the gas that roasting generates generates the high regenerating acid of hydrofluoric acid concentration after Selective absorber tower absorbs, be back to spent acid storage tank and freezing and crystallizing tank, by regulating the fluorinion concentration in spent acid storage tank and freezing and crystallizing tank after the regenerating acid backflow that hydrofluoric acid containing concentration is high.
8. the full acid regeneration method of a kind of stainless steel acid-washing waste liquid as claimed in claim 1, it is characterized in that, in regenerating acid storing step, the storage tank of regenerating acid can adopt three tank forms, deposit high concentration of hydrofluoric acid recovered acid for one, deposit the high recovered acid of concentration of nitric acid for one, deposit nitric acid and the acid of hydrofluoric acid mixed regeneration for one.
9. the full acid regeneration method of a kind of stainless steel acid-washing waste liquid as claimed in claim 1, it is characterized in that, in the process and vent gas treatment step of brown iron oxide, the burning iron powder that calcination furnace bottom generates is packed by pelletizer, and the tail gas that absorption tower cannot absorb enters denitrification processing device.
10. a full acid regeneration device for stainless steel acid-washing waste liquid, it mainly comprises spent acid storage tank, freezing and crystallizing tank, temperature control surge tank, recovered acid tank, absorption tower and stoving oven; It is characterized in that, spent acid storage tank is connected with freezing and crystallizing tank by pipeline, freezing and crystallizing tank is connected with temperature control surge tank by pipeline, temperature control surge tank is connected with recovered acid tank respectively by high pressure fluid infusion pump and recycle pump, recovered acid tank is connected with spent acid storage tank with absorption tower by pipeline, absorption tower is connected with stoving oven by pipeline, and stoving oven is connected by the out of stock device of pipeline and desulfurization, and stoving oven is connected with brown iron oxide collection device by pipeline.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104674260A (en) * | 2015-03-30 | 2015-06-03 | 山东钢铁股份有限公司 | Rapid control method for preventing regenerated waste cold rolled steel pickling acid from crystallization |
| CN105859005A (en) * | 2016-05-10 | 2016-08-17 | 宝钢工程技术集团有限公司 | Method and system for treating stainless steel cold-rolling and pickling waste acid |
| CN107460493A (en) * | 2017-07-04 | 2017-12-12 | 当涂县宏宇金属炉料有限责任公司 | A kind of recovery and treatment method of secondary metal pickle liquor |
| CN107574450A (en) * | 2017-10-20 | 2018-01-12 | 鞍山创新废酸除硅再生工程有限公司 | A kind of stainless steel acid-washing waste liquid renovation process and system |
| CN110330199A (en) * | 2019-07-29 | 2019-10-15 | 中冶南方工程技术有限公司 | A kind of stainless steel mixed acid waste liquor sludge harmless treatment method |
| CN113774213A (en) * | 2021-08-16 | 2021-12-10 | 中冶南方工程技术有限公司 | Recycling method and system of stainless steel mixed acid pickling sludge |
| CN114230050A (en) * | 2021-12-31 | 2022-03-25 | 宝武水务科技有限公司 | Method and system for treating cold rolling pickling wastewater |
| CN114230050B (en) * | 2021-12-31 | 2024-05-03 | 宝武水务科技有限公司 | Cold rolling pickling wastewater treatment method and system |
-
2013
- 2013-06-27 CN CN201310264610.8A patent/CN104250820A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104674260A (en) * | 2015-03-30 | 2015-06-03 | 山东钢铁股份有限公司 | Rapid control method for preventing regenerated waste cold rolled steel pickling acid from crystallization |
| CN105859005A (en) * | 2016-05-10 | 2016-08-17 | 宝钢工程技术集团有限公司 | Method and system for treating stainless steel cold-rolling and pickling waste acid |
| CN107460493A (en) * | 2017-07-04 | 2017-12-12 | 当涂县宏宇金属炉料有限责任公司 | A kind of recovery and treatment method of secondary metal pickle liquor |
| CN107574450A (en) * | 2017-10-20 | 2018-01-12 | 鞍山创新废酸除硅再生工程有限公司 | A kind of stainless steel acid-washing waste liquid renovation process and system |
| CN110330199A (en) * | 2019-07-29 | 2019-10-15 | 中冶南方工程技术有限公司 | A kind of stainless steel mixed acid waste liquor sludge harmless treatment method |
| CN113774213A (en) * | 2021-08-16 | 2021-12-10 | 中冶南方工程技术有限公司 | Recycling method and system of stainless steel mixed acid pickling sludge |
| CN114230050A (en) * | 2021-12-31 | 2022-03-25 | 宝武水务科技有限公司 | Method and system for treating cold rolling pickling wastewater |
| CN114230050B (en) * | 2021-12-31 | 2024-05-03 | 宝武水务科技有限公司 | Cold rolling pickling wastewater treatment method and system |
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